J Fluoresc
2-(2-Methyl-6,11-Dioxo-6,11-Dihydronaphtho[2,3-b]
Indolizine-12-Carbonyl)Benzoic Acid (4c)
479 (3.51). 1H-NMR (DMSO-d6), δ, ppm (J, Hz): 7.58–7.62
(3 H, m), 7.75 (2 H, d, J = 6.4), 7.82–7.86 (2 H, m), 8.00 (1 H,
dd, J = 1.6, 7.3), 8.14 (1 H, d, J = 7.3), 8.34 (2 H, d, J = 6.2),
8.73 (1 H, s), 8.98 (2 H, d, J = 6.2), 9.84 (1 H, d, J = 7.3),
12.82–12.86 (1 H, br. s). 13C-NMR (DMSO-d6), δ: 115.4;
117.2; 120.1; 122.4; 123.8; 126.4; 127.1; 128.2; 128.5;
128.8; 128.9; 129.4; 130.9; 131.2; 131.5; 132.4; 133.5;
133.8; 134.2; 134.7; 135.5; 139.3; 142.3; 145.2; 150.2;
169.0 (C = O); 175.2 (C = O); 180.2 (C = O); 191.8 (C = O)
ppm. Found, %: C 73.59; H 3.23; N 5.77. C29H16N2O5.
Calcd., %: C 73.73; H 3.41; N 5.93.
Rf = 0.82, yield 61 %, mp 264 °C. IR, ν, cm−1: 1618, 1672,
1716, 2638, 3080. UV (CHCl3), λmax, nm (lg ε): 335 (4.19),
504 (3.79). 1H-NMR (DMSO-d6), δ, ppm (J, Hz): 2.50 (3 H,
s), 7.37 (1 H, dd, J = 1.7, 7.1), 7.55–7.64 (3 H, m), 7.68–7.74
(2 H, m), 7.79 (1 H, dd, J = 1.5, 4.7), 7.83 (1 H, dd, J = 1.7,
7.1), 8.11 (2 H, d, J = 7.6), 9.68 (1 H, d, J = 7.1), 12.65–12.80
(1 H, br. s). 13C-NMR (DMSO-d6), δ, ppm: 21.7 (CH3);
112.5; 119.5; 121.5; 121.6; 126.1; 126.9; 127.8; 128.0;
128.6; 129.5; 130.5; 131.5; 132.2; 133.5; 133.7; 133.8;
134.5; 140.6; 141.8; 142.9; 169.0 (C = O); 174.4 (C = O);
180.5(C = O); 191.7 (C = O). Found, %: C 72.99; H 3.66; N
3.36. C25H15NO5. Calcd., %: C 73.35; H 3.69; N 3.42.
12-(2-Carboxybenzoyl)
-6,11-Dioxo-6,11-Dihydronaphtho[2,3-b]
Indolizine-2-Carboxylic Acid (4 g)
2-(2-t-Butyl-6,11-Dioxo-6,11-Dihydronaphtho[2,3-b]
Indolizine-12-Carbonyl)Benzoic Acid (4d)
Rf = 0.18, yield 63 %, mp 307 °C. IR, ν, cm−1: 1627, 1673,
1689, 2658, 2821, 3103. UV (DMF), λmax, nm (lg ε): 337
1
(3.56), 478 (3.21). H-NMR (DMSO-d6), δ, ppm (J, Hz):
Rf = 0.30, yield 59 %, mp 252 °C. IR, ν, cm−1: 1620, 1674,
1698, 2967, 3410. UV (CHCl3), λmax, nm (lg ε): 335 (4.29),
507 (3.85). 1H-NMR (DMSO-d6), δ, ppm (J, Hz): 1.36 (9 H,
s), 7.54–7.56 (3 H, m), 7.66 (1 H, dd, J = 2.0, 7.4), 7.78 (4 H,
qd, J = 7.7, 13.7), 8.14 (2 H, m), 9.69 (1 H, d, J = 7.3), 12.75–
12.86 (1 H, br. s). 13C-NMR (DMSO-d6), δ: 30.3 (CH3); 35.6;
112.9; 115.3; 118.5; 121.6; 126.2; 126.9; 127.9; 128.2; 128.5;
129.4; 130.5; 131.5; 132.5; 133.6; 133.8; 133.9; 134.5; 140.4;
143.1; 153.8; 168.9 (C = O); 174.6 (C = O); 180.5 (C = O);
191.74 (C = O) ppm. Found, %: C 74.38; H 4.43; N 2.92.
C28H21NO5. Calcd., %: C 74.49; H 4.69; N 3.10.
7.62 (3 H, dd, J = 2.0, 7.4), 7.75 (2 H, dd, J = 3.3, 6.1), 7.81
(2 H, m), 7.88 (1 H, d, J = 6.9), 8.17 (2 H, d, J = 7.9), 9.82
(1 H, dd, J = 1.1, 7.3), 12.82–12.90 (1 H, br. s), 13.60–13.80
(1 H, br. s). 13C-NMR (DMSO-d6), δ: 120.7; 122.42; 127.63;
128.01; 131.2; 131.9; 133.2; 133.9; 135.5; 135.7; 136.4;
138.2; 138.6; 139.0; 139.5; 143.5; 143.6; 145.8; 147.1;
155.7; 170.5 (C = O); 173.8 (C = O); 180.0 (C = O); 185.0
(C = O); 196.7 (C = O) ppm. Found, %: C 68.17; H 2.76; N
3.01. C25H13NO7. Calcd., %: C 68.34; H 2.98; N 3.19.
Method for the preparation of compounds 6a,b: 2,3-
Dichloro-1,4-naphthoquinone (1.0 g, 4.4 mmol) and bindone
(1.21 g, 4.4 mmol) were dissolved in acetonitrile (50 ml).
Solution was refluxed for 1 h and then 1 eq. of H2O2 (30 %
aqueous solution) was added to a stirring solution. After
15 min pyridine 3a or 3b was added (8.8 mmol) and reaction
mixture was refluxed for 2–4 h. The rate of the reaction was
followed by TLC. Reaction mixture was cooled to room tem-
perature and kept at this temperature for 24 h. The black pre-
cipitate that formed was filtered. Pure product can be obtained
by recrystallization from ethanol.
Inner salt 6a: Rf = 0.18, yield 62 %, mp > 300 °C. λmax
(CHCl3) nm (lg ε): 503 (4.04), 535 (3.98), 742 (3.79). λmax
(DMF) nm: 498, 527, 704. 1H-NMR (CDCl3), δ, ppm (J, Hz):
7.23 (1 H, m), 7.43 (1 H, m), 7.49 (2 H, m), 7.60 (1 H, m), 7.69
(1 H, dd, J = 1.5, 7.4), 7.73 (2 H, dd, J = 1.7, 3.2), 7.77 (1 H, dd,
J = 1.5, 7.4), 7.80 (1 H, m), 8.02 (2 H, dt, J = 3.9, 7.6), 8.19 (1 H,
dd, J = 1.3, 7.6), 8.32 (1 H, m), 8.83 (1 H, d, J = 7.7), 9.07 (1 H,
d, J = 6.1), 9.48 (1 H, d, J = 6.0). 13C-NMR (CDCl3), δ: 120.5;
121.3; 125.0; 126.0; 126.1; 126.6; 127.7; 128.7; 130.1; 130.8;
131.5; 132.5; 132.6; 133.0 (2C); 133.1; 133.8; 134.2; 135.1;
140.9; 142.1; 143.0; 144.6; 145.1; 146.7; 148.0; 150.1; 160.1;
162.3; 177.8 (C = O); 180.2 (C = O); 197.5 (C = O); 218.4
(C = O) ppm. Found, %: C 77.97; H 3.17; N 2.59.
C33H17NO5. Calcd., %: C 78.10; H 3.38; N 2.76.
2-(8,13-Dioxo-8,13-Dihydro [5, 6]Indolo[2,1-a]
Isoquinoline-14-Carbonyl)Benzoic Acid (4e)
Rf = 0.63, yield 67 %, mp 293 °C. IR, ν, cm−1: 1640, 1667,
1744, 2652, 3064. UV (CHCl3), λmax, nm (lg ε): 306 (4.33),
470 (3.56). 1H-NMR (DMSO-d6), δ, ppm (J, Hz): 7.48 (1 H,
d, J = 8.6), 7.54 (1 H, d, J = 7.6) 7.64 (2 H, d, J = 4.4), 7.68
(2 H, d, J = 7.0), 7.80 (2 H, d, J = 7.8), 7.95 (3 H, m), 8.19
(2 H, dd, J = 4.2, 7.7), 9.45 (1 H, d, J = 7.4), 13.15–13.25 (1 H,
br. s). 13C-NMR (DMSO-d6), δ: 116.6; 118.3; 122.8; 124.1;
124.5; 125.2; 126.7; 126.8; 127.6; 128.3; 128.4; 129.3; 129.8;
130.0; 130.4; 132.0; 133.1; 133.2; 133.8; 134.1; 134.5; 134.7;
135.8; 135.9; 170.9 (C = O); 175.0 (C = O); 180.7 (C = O);
193.3 (C = O). Found, %: C 75.33; H 3.33; N 3.05.
C28H15NO5. Calcd., %: C 75.50; H 3.39; N 3.14.
2-(6,11-Dioxo-2-(Pyridin-4-yl)
-6,11-Dihydronaphtho[2,3-b]Indolizine-12-Carbonyl)
Benzoic Acid (4f)
Rf = 0.40, yield 68 %, mp 320 °C. IR, ν, cm−1: 1630, 1669,
1700, 2626, 3066. UV (DMF), λmax, nm (lg ε): 340 (3.81),